Metallized formazan compounds having two fiber reactive groups linked by n-alkyl-containing group

ABSTRACT

A reactive metal formazan blue dye represented by a free acid of the formula, ##STR1## wherein A 1  and A 2  are independently a substituted or unsubstituted phenylene or naphthylene group, B is a straight or branched alkyl or alkenyl group, a phenyl group, a naphthyl group or a heterocyclic group, the alkyl, alkenyl, phenyl, napthyl and heterocyclic group being substituted or unsubstituted, Me is an ion of metal identified by an atomic number of 27 to 29, X is --O-- or ##STR2## Y is a halogen atom, Z is a group capable of imparting water solubility, each of l, m and n is 0 or an integer of 1 to 3, provided that the sum of l, m and n is from 1 to 4, D is a substituted or unsubstituted phenylene or naphthylene group, R is a substituted or unsubstituted lower alkyl group, and Q is --SO 2  CH═CH 2  or --SO 2  CH 2  CH 2  L in which L is a group capable of being splitted by the action of alkali, which is useful for dyeing hydroxy- or amido-containing fiber materials with good build-up and level-dyeing properties to obtain a dyed product of deep blue color having excellent fastness, particularly against light, perspiration-light and chlorine.

The present invention relates to a metal formazan compound, a method forproducing the same and a method for dyeing fiber materials by using thesame.

More specifically, the present invention relates to a metal formazancompound, particularly a copper formazan compound, a method forproducing the same and a method for dyeing fiber materials in a bluecolor by using the same as a fiber-reactive dye.

Reactive metal formazan dyes having a manohalogenotriazinyl group, asulfatoethylsulfonyl group or the like as a fiber-reactive group areknown. Recently, reactive dyes of this kind having two reactive groupsdifferent from each other have been developed to improve the dyeperformances. However, these reactive dyes are still insufficient intheir dye performances such as fixing efficiency, dyeing velocity,level-dyeing property, solubility, fastness or the like.

For example, Published Unexamined Japanese Patent Application No.4783/1981 discloses a dye of the following formula (A), ##STR3## whichis unsatisfactory in fixing efficiency and solubility (particularly whenthe sulfatoethylsulfonyl group is converted to vinylsulfonyl group bythe action of alkali). U.S. Pat. No. 3,926,942 discloses a dye of thefollowing formula (B), ##STR4## which is insufficient in the fixingefficiency as well as acid-hydrolysis fastness and reproducibility ofdyed Published Unexamined Japanese Patent Application No. 12187/1980also discloses a dye of the following formula (C), ##STR5## which isalso insufficient in the fixing efficiency and solubility. The presentinventors have studied to solve the above problems in the metal formazanreactive dyes having two reactive groups different from each other inthe molecule, and found the fact that the linking group between themonohalogenotriazinyl group and the aromatic group to which thesulfatoethylsulfonyl group is appended decisively affects various dyeperformances, and that the problems described above can be solved byselecting a suitable linking group. The present invention provides acompound represented by a free acid of the formula (I), ##STR6## whereinA₁ and A₂ are independently a substituted or unsubstituted phenylene ornaphthylene group, B is a straight or branched alkyl or alkenyl group, aphenyl group, a naphthyl group or a heterocyclic group, the alkyl,alkenyl, phenyl, naphthyl and heterocyclic group being substituted orunsubstituted, Me is an ion of metal identified by an atomic number of27 to 29, X is --O-- or ##STR7## Y is a halogen atom, Z is a groupcapable of imparting water solubility, each of 1, m and n is O or aninteger of 1 to 3, provided that the sum of 1, m and n is from 1 to 4, Dis a substituted or unsubstituted phenylene or naphthylene group, R is asubstituted or unsubstituted lower alkyl group, and Q is --SO₂ CH=CH₂ or--SO₂ CH₂ CH₂ L in which L is a group capable of being splitted by theaction of alkali, a method for producing the above compound of theformula (I), which comprises

(1) subjecting a 1,3,5-trihalogeno-s-triazine to first-step condensationwith a formazan compound of the formula (II), ##STR8## wherein A₁, A₂,B, Me, X, Z, l, m and n are as defined above, and then to second-stepcondensation with a compound of the formula (III), ##STR9## wherein D, Rand Q are as defined above, or

(2) subjecting a 1,3,5-trihalogeno-s-triazine to first-step condensationwith the compound of the formula (III), and then to second-stepcondensation with the formazan compound of the formula (II), and also amethod for dyeing fiber materials, which comprises using the compound ofthe formula (I).

In the above formula (I), the substituent of the phenylene ornaphthylene group represented by A₁ and A₂ includes a halogen atom and anitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, sulfamoyl, N-mono- or N,N-di-C₁ -C₄alkylsulfamoyl, C₁ -C₄ alkylsulfonyl and phenylsulfonyl groups and thelike. Of these substituted phenylene and naphthylene groups, preferredare phenylene groups substituted with one or two (preferably one)substituents selected from the group consisting of chlorine and bromineatoms and nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl andN,N-dimethylsulfamoyl groups.

The straight or branched alkyl and alkenyl groups represented by B arepreferably those having 1 to 8, preferably 2 to 8, carbon atoms. Thesubstituent which may be appended to the alkyl and alkenyl groupsincludes a phenyl group unsubstituted or substituted with at least onemember selected from the group consisting of halogen atoms and methyl,ethyl, methoxy, ethoxy and sulfamoyl groups. The substituent of thephenyl and naphthyl groups represented by B includes a halogen atom andhydroxy, nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and carbo-C₁ -C₄ -alkoxygroups and the like. The heterocyclic group represented by B includes aresidue of furan, thiophene, pyrrole, imidazole, indole, pyrazole,pyridine, pyrimidine, quinoline, benzimidazole or the like. To thearomatic carbon atom constituting the heterocyclic group, a chlorineatom or a phenyl, methyl, ethyl, methoxy or ethoxy group or the like maybe appended, and the hydrogen atom of --NH-- in the heterocyclic groupmay be substituted by a methyl, ethyl or benzyl group. Of these groupsrepresented by B, preferred are phenyl groups unsubstituted orsubstituted with one or two members selected from the group consistingof a chlorine atom and methyl, ethyl, methoxy, ethoxy, carbomethoxy,carboethoxy and nitro groups.

Among ions of the metal identified by an atomic number of 27 to 29represented by Me, a preferable metal ion is copper ion.

The halogen atom represented by Y includes fluorine, chlorine andbromine atoms. Of these, preferred are fluorine and chlorine atoms.

The group capable of imparting water solubility, which is represented byZ, includes sulfonic acid, carboxylic acid and phosphoric acid groups.Of these, sulfonic acid group is preferred. These groups are appended tothe aromatic or aliphatic carbon atom of the phenylene, naphthylene,alkyl, alkenyl, phenyl, naphthyl or heterocyclic group represented byA₁, A₂, or B, or to that of the substituent thereof.

The substituent which may be appended to the phenylene group representedby D includes C₁ -C₄ alkyl and C₁ -C₄ alkoxy groups and halogen atoms.Of these, preferred are methyl, ethyl, methoxy and ethoxy groups andchlorine and bromine atoms. The substituent which may be appended to thenaphthylene group represented by D includes a sulfonic acid group.

The lower alkyl group represented by R includes methyl, ethyl, propyland butyl groups and the like. The substituent thereof includeshydroxyl, carboxy, sulfo, carbamoyl, cyano and methoxycarbonyl groupsand the like. Preferred R includes methyl, ethyl, carbamoylethyl,hydroxyethyl and n- or iso-propyl groups.

Preferred X is a carbonyloxy group ##STR10##

The sum of 1, m and n is preferably 2 or 3.

In the case where Q in the formula (I) stands for --SO₂ CH₂ CH₂ L, thegroup L capable of being split by the action of alkali includes ahalogen atom such as chlorine and bromine atoms, an ester group of anorganic carboxylic or sulfonic acid such as a lower alkanoyloxy groupincluding acethyloxy group, a benzoyloxy group and a benzene-sulfonyloxygroup, and a group represented by a free acid of the formula, --OPO₃ H₂,--SSO₃ H or --OSO₃ H. Of these groups, --OSO₃ H is particularlypreferred. Thus, preferred Q is --SO₂ CH₂ CH₂ OSO₃ H, which may bepartially replaced by --SO₂ CH=CH₂.

In the formula (I), the group represented by the following formula,##STR11## wherein Y, R, D and Q are as defined above, may be appended toany one of the aromatic or aliphatic carbon atom of the phenylene,naphthylene, alkyl, alkenyl, phenyl, naphthyl or heterocyclic grouprepresented by A₁, A₂ or B, or to that of the substituent thereof. Ofthese groups to which the group of the above formula is appended, thephenylene or phenyl group is preferred.

Among the metal formazan compounds represented by the foregoing formula(I), a preferable compound is a compound represented by a free acid ofthe following formula, ##STR12## wherein R and Q are as defined above,D₁ is a phenylene group unsubstituted or substituted with a methyl,ethyl, methoxy or ethoxy group or a chlorine or bromine atom, or anaphthylene group unsubstituted or substituted with a sulfonic acidgroup, Y₁ is a fluorine or chlorine atom, and each of p, q and r isindependently 0 or 1, provided that the sum of p, q and r is from 1 to3. Of these, a more preferable compound is a compound represented by afree acid of the following formula ##STR13## wherein R, D₁, Q, Y₁, p andq are as defined above. A still more preferable is a compoundrepresented by a free acid of the following formula, ##STR14## wherein Qis as defined above, and R₁ is a methyl group or CH₂ CH₂ W in which W isa hydrogen atom or a methyl, ethyl, hydroxyl, carbamoyl, cyano, carboxyor sulfo group.

The metal formazan compounds described above are preferably in the formof an alkali metal or alkaline earth metal salt, more specificallysodium or potassium salt.

The metal formazan compound of the formula (I) can be produced bysubjecting a 1,3,5-trihalogeno-s-triazine to first-condensation with anyone of the formazan compound of the formula (II) or the compound of theformula (III), followed by second-condensation with the other.

In this process, the order of the condensation reaction is notparticularly limited, and the reaction conditions are also notparticularly limited. In general, the reaction may be carried out at apH of 2 to 8, preferably 3 to 6, and at a temperature of -5° to 50° C.,perferably 0° to 40° C.

Considering the reaction yield and the quality of the desired metalformazan compound of the formula (I), it is preferable to carry out thefirst-condensation using any one compound of the formula (II) or (III)having a lower reactivity to the 1,3,5-trihalogeno-s-triazine than theother.

In the first-condensation reaction, although the reaction conditions maybe determined depending on the stability of the starting compound andintermediate compound to be produced, the reaction may be carried out ata relatively low pH ranging from 2 to 4, preferably from 3 to 4, and ata relatively low temperature ranging from -5° to 20° C., preferably from0° to 10° C.

In the second-condensation reaction, the reaction conditions may bedetermined depending on the stability of the starting compound, theintermediate and the desired metal formazan compound. For example, thereaction may be carried out at a relatively high pH ranging from 4 to 8,preferably from 4 to 6, and at a relatively high temperature rangingfrom 20° to 50° C., preferably from 30° to 40° c.

The starting formazan compound of the formula (II) can be obtained froma compound represented by the formula (IV), ##STR15## wherein A₁, A₂, B,Me, X, Z, l, m and n are as defined above, and T is a nitro (--NO₂),acetylamino (--NHCOCH3) group or the like, which is appended to thearomatic or aliphatic carbon atom of any group represented by A₁, A₂ orB, or to that of the substituent thereof. For the preparation of thecompound (II), the above compound (IV) is subjected to reduction (whenT=--NO₂) or hydrolysis (when T=--NHCOCH₃) in a conventional manner.

The compound of the above formula (IV) can be prepared, for example, inthe following manner.

A diazonium compound prepared by diazotizing an aromatic aminerepresented by the following formula (V), ##STR16## wherein A₁, X, Z andm are as defined above, is allowed to react with a sulfite to obtain anN-sulfonic acid, the N-sulfonic acid is subjected to hydrolyzation witha mineral acid, the resulting hydrazine compound is allowed to reactwith an aldehyde compound represented by the formula (VI),

    Z.sub.n -B-CHO                                             (VI)

wherein B, Z and n are as defined above, to obtain a hydrozone compound,and then the hydrazone compound is subjected to coupling with adiazonium compound of an aromatic amine of the formula (VII), ##STR17##wherein A₂, Z and l are as defined above, during or after the coupling acompound capable of imparting a metal ion (Me), such as metal sulfates,metal carbonates, metal acetates, metal salicylates, metal tartaratesand metal chlorides being added thereto to form the corresponding metalcomplex, which is simultaneously or successively treated with an acid oran alkali, whereby the desired compound (IV) is obtained, provided thatany one of the compounds (V), (VI) and (VII) to be used in the abovemanner has the substituent, --NO₂ or --NHCOCH3, which is represented byT.

Examples of the aromatic amine of the formula (V) usable for thepreparation of the compound (IV) are as follows:

2-Aminophenol

4- or 5-Methyl-2-aminophenol

4- or 5-Sulfo-2-aminophenol

4-Sulfo-6-carboxy-2-aminophenol

4-Methoxy-2-aminophenol

5-Methylsulfonyl-2-aminophenol

4-Mono- or dimethylsulfamoyl-2-aminophenol

5-Nitro-2-aminophenol

4-Bromo-2-aminophenol

4,6-Disulfo-2-aminophenol

2-Acetylamino-6-aminophenol-4-sulfonic acid

6-Nitro-4-sulfo-2-aminophenol

4-Nitro-6-sulfo-2-aminophenol

4-Acetylamino-6-sulfo-2-aminophenol

4-Chloro-6-sulfo-2-aminophenol

6-Chloro-4-sulfo-2-aminophenol

4-Methylsulfonyl-2-aminophenol

4-Butylsulfonyl-2-aminophenol

4-Ethylsulfonyl-2-aminophenol

4-Sulfamoyl-2-aminophenol

1-Amino-2-hydroxynaphthalene-4,6-disulfonic acid

1-Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid

1-Amino-2-hydroxy-6-chloronapthahlene-4-sulfonic acid

2-Aminobenzoic acid

4- or 5-Sulfo-2-aminobenzoic acid

5-Nitro-2-aminobenzoic acid

4- or 5-Chloro-2-aminobenzoic acid

4-Methoxy-2-aminobenzoic acid

4- or 5-Acetylamino 2-aminobenzoic acid

2,5-Dicarboxyaniline

4-Methyl-6-sulfo-2-aminophenol

Examples of the aldehyde of the formula (VI) usable for the preparationof the compound (IV) are as follows:

Benzaldehyde

2-, 3- or 4-Methylbenzaldehyde

4-Methylbenzaldehyde-3-sulfonic acid

2-, 3- or 4-Methoxybenzaldehyde

4-Methoxy-3-chlorobenzaldehyde

2- or 3-Nitrobenzaldehyde

2-Hydroxybenzaldehyde

2- or 4-Chlorobenzaldehyde

2,4-Dichlorobenzaldehyde

2-Chlorobenzaldehyde-5-sulfonic acid

Benzaldehyde-2-sulfonic acid

Benzaldehyde-3-sulfonic acid

Benzaldehyde-4-sulfonic acid

Benzaldehyde-2,4-disulfonic acid

2- or 4-Acetylaminobenzaldehyde

4-Nitrobenzaldehyde-2-sulfonic acid

3-Methyl-2- or 6-nitrobenzaldehyde

2-Chloro-6-nitrobenzaldehyde

1-Naphthoaldehyde

2-Naphthoaldehyde

Furan-2-aldehyde

Thiophene-2-aldehyde

Pyrrole-2-aldehyde

Imidazole-2-aldehyde

Pyrazole-5-aldehyde

Pyridine-2-aldehyde

Pyridine-3-aldehyde

Pyridine-4-aldehyde

Pyrimidine-5-aldehyde

Quinoline-4-aldehyde

Benzimidazole-2-aldehyde

Acetaldehyde

Propionaldehyde

Butyraldehyde

Enanthaldehyde

Acrylaldehyde

Crotonaldehyde

Phenacetaldehyde

Cinnamaldehyde

Examples of the aromatic amine compound (VII) usable for the preparationof the compound (IV) are the same as those of the compound (V) excludingthose having a carbonyloxy group ##STR18## as X in the formula (V).

The aromatic amine represented by the foregoing formula (III) can beprepared by reacting an aromatic amine compound represented by theformula (VIII),

    H.sub.2 N-D-Q                                              (VIII)

wherein D and Q are as defined above, with an alkylating agent describedbelow, or by alkylating a precursor for the amine compound (VIII)represented by the formula (IX),

    H.sub.2 N-D-SO.sub.2 CH.sub.2 CH.sub.2 OH                  (IX)

wherein D is as defined above, in the same manner as described above,followed by esterification or halogenation in a conventional manner.

The alkylating agent includes alkyl halides, dialkylsulfuric acids,mono-substituted ethylenes and oxides, from which a suitable one may bechosen depending on the kind of R in the foregoing formula (III).Examples thereof are as follows:

The alkyl halides include, for example, methyl-, ethyl-, n- or iso-propyl-, n-, iso- or sec-butyl-bromides and iodides.

The mono-substituted ethylenes include, for example, acrylonitrile,acrylic acid, methyl or ethyl acrylate, acrylamide and vinylsulfonicacid.

The dialkylsulfuric acids include, for example, dimethylsulfuric acidand diethylsulfuric acid.

The oxides include, for example, ethylene oxide, propylene oxide,glycidol, trimethylene oxide, β-butylene oxide, 2-methyl-α-bytyleneoxide, 2-ethyl-3-methylethylene oxide, methoxyethylene oxide andn-butoxyethylene oxide.

Examples of the aromatic amine compounds (VIII) are as follows:

1-Aminobenzene-2,3- or 4-β-sulfatoethylsulfone

1-Aminobenzene-3-phosphatoethylsulfone

10 1-Amino-4-methylbenzene-3-β-sulfatoethylsulfone

1-Aminobenzene-3-β-chloroethylsulfone

1-Amino-4-methoxybenzene-3-β-sulfatoethylsulfone

1-Amino-2,5-dimethoxybenzene-4-8-sulfatoethyl

1-Amino-2-methoxybenzene-4-β-sulfatoethylsulfone

1-Amino-2-chlorobenzene-4-β-sulfatoethylsulfone

1-Amino-2-methoxybenzene-5-β-sulfatoethylsulfone

2-Aminonaphthalene-8-β-sulfatoethylsulfone

2-Aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid

1-Amino-2,5-dimethoxybenzene-4-vinylsulfone

1-Amino-2-methoxy-5-methylbenzene-4-5-sulfatoethylsulfone

2-Aminonaphthalene-4-, 5-, 6- or 7-β-sulfatoethylsulfone

1-Amino-2-bromobenzene 4-β-sulfatoethylsulfone

1-Amino-2-bromobenzene-4-vinylsulfone

2-Amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone

1 2-Aminonapthhalene-8-β-phosphatoethylsulfone-6-sulfonic acid

2-Aminonaphthalene-8-vinylsulfone-6-sulfonic

1-Amino-2-methoxy-5-methylbenzene-4-β-chloroethylsulfone

1-Aminobenzene-2-, 3- or 4-vinylsulfone

1-Amino-2-methoxy-5-chlorobenzene-4-β-sulfato ethylsulfone or-4-vinylsulfone

1-Amino-2-ethoxy-5-chlorobenzene-4-β-sulfatoethylsulfone or-4-vinylsulfone

2-Aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid

5-Chloroaniline-2-β-sulfatoethylsulfone

5-Sulfoaniline-2-β-sulfatoethylsulfone

Aniline-2-β-thiosulfatoethylsulfone

5-Chloroaniline-2-β-thiosulfatoethylsulfone

5-Sulfoaniline-2-β-thiosulfatoethylsulfone

Aniline-2-β-phosphatoethylsulfone

5-Chloroaniline-2-β-phosphatoethylsulfone

5-Sulfoaniline-2-β-phosphatoethylsulfone

5-Chloroaniline-2-vinylsulfone

5-Sulfoaniline-2-vinylsulfone

Aniline-2-β-chloroethylsulfone

5-Chloroaniline-2-β-chloroethylsulfone

5-Sulfoaniline-2-β-chloroethylsulfone

All the starting compounds described above may be used in the form ofacid or salts, particularly alkali metal salts or alkaline earth metalsalts.

The metal ion of the present metal formazan compound can be given asdesired by selecting the kind of the starting compounds, alkali agentsusable for neutralization of the acid during the formazan metal compoundproduction steps, or electrolytes to be used when the desired compoundis, if desired, isolated by salting-out.

The metal formazan compound produced in accordance with the presentinvention may be in a liquid form obtained by removing inorganic saltsor adding a dyeing improver, if necessary, after completion of thereaction, or may be formed into a powdery product by subjecting theabove liquid or the reaction mixture as such to evaporation i.e.spray-drying and the like, or into either liquid or powdery productthrough salting out of the desired compound in a conventional mannerusing an electrolyte.

The metal formazan compound of the formula (I) having two kinds of fiberreactive groups may be used as a reactive dye for dyeing hydroxylgroup-, or amido group-containing materials.

The hydroxyl group-containing materials include natural or synthetichydroxyl group-containing fiber materials such as cellulose fibermaterials, regenerated products thereof and polyvinyl alcohol. Examplesof the cellulose fiber materials are cotton and other vegetable fiberssuch as linen, hemp, jute and ramie fibers. Examples of the regeneratedcellulose fibers are viscose staple and filament viscose.

The amido group-containing materials include synthetic or naturalpolyamide and polyurethane. Examples of the materials, particularly inthe fibrous forms, are wool and other animal furs, silk, leather,polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The dyeing may be carried out in a manner suitable for the reactivegroups appended to the fiber-reactive dye.

For example, in the case of dyeing cellulose fiber materials, the dyeingmay be carried out by an exhaustion dyeing, printing, padding includingcold-pad-batch-up method or the like, from which a suitable one may bechosen depending on the property and physical form of the fibers. Inthese methods, an acid-binding agent such as sodium hydroxide, sodiumcarbonate, sodium bicarbonate, phosphates, silicates and the like may beused together with the metal formazan compound of the formula (I).

More concretely speaking, the exhaustion dyeing may be carried out at arelatively low temperature using a dye bath containing sodium hydroxideor other acid-binding agents, and sodium sulfate or sodium chloride. Theprinting may be carried out by preparing a dye paste containing a pasteor emulsified paste such as sodium alginate and starch ether, alkalis oralkali-liberating agents such as sodium carbonate, sodium bicarbonate,sodium hydroxide, trisodium phosphate, sodium trichloroacetate and thecorresponding potassium or alkaline earth metal salts, and if desired, aconventional printing assistant such as urea, and a dispersing agent,applying the dye paste on the fiber, drying and then heat-treating theprinted fiber using steam. The cold-pad-batch-up method may be carriedout by applying a padding solution to the fiber at ambient temperature,the padding solution comprising an acid-binding agent such as sodiumhydroxide alone or a mixture of sodium hydroxide and sodium silicate,sodium carbonate or trisodium phosphate, and if necessary, a dissolvingassistant such as urea, and a penetrant, batching up the fiber with aroll, allowing to stand for 3 hours or more, or overnight, and thenrinsing and drying to obtain a dyed product.

The metal formazan compound of the present invention can give remarkableadvantages in the dyeing of fiber materials. Particularly when used fordyeing cellulose fiber materials, the present compounds, particularlycopper formazan compounds, can exhibit excellent build-up andlevel-dyeing properties and give a dyed product excellent in lightfastness, perspiration-light fastness, abrasion fastness, wet fastnesssuch as washing resistance, chlorine-containing water resistance,chlorine-bleaching resistance, alkali resistance, perspirationresistance and peroxide-washing resistance, acid-hydrolysis fastness andiron fastness.

Further, the present compounds are superior in dischargeability toanthraquinone dyes, and are suitable as a blue dye of three-primarycolor.

Furthermore, the present compounds can give a dyed product constant inthe quality irrespective of change in the dyeing temperature, andexhibit high exhaustion and fixation percentages, and improvedsolubility in water or alkali-containing water.

The present invention is illustrated in more detail with reference tothe following Examples which are only illustrative of the presentinvention. In Examples, parts are by weight.

EXAMPLE 1

A mixture of concentrated hydrochloric acid (67 parts),2-carboxyphenylhydrazine-5-sulfonic acid (23.2 parts) and benzaldehyde(11.0 parts) in water (100 parts) was stirred at 55° C. overnight toobtain a hydrazone compound.

On the other hand, a solution consisting of water (50 parts),3-acetylamino-2-hydroxyaniline-5-sulfonic acid (24.6 parts) andconcentrated hydrochloric acid (28.2 parts) was cooled to 0° to 10° C.,and a solution of sodium nitrite (7.1 parts) in water (18 parts) wasadded to the above solution. The mixture was stirred for 1 to 2 hours atthat temperature, and thereafter excess nitrous acid was decomposed toobtain a diazo compound.

This diazonium compound was mixed with the above hydrazone compound, andthe mixture was stirred in the presence of sodium carbonate at 0° to 5°C. until the diazonium compound disappeared. The formazan-containingreaction mixture was adjusted to pH of between 5 and 6, and then mixedwith crystalline copper sulfate (26.2 parts). The mixture was stirredfor about 5 hours at a temperature of between 40° and 50° C. to obtain acopper complex compound, which was then isolated by salting-out usingsodium chloride. The isolated compound was kept in a 3% aqueous sodiumhydroxide solution for about 10 hours at 90° C. to hydrolyze theacetylamino group.

The resulting mixture was adjusted to pH of between 3 and 4, and thenmixed with cyanuric chloride (16.6 parts). The mixture was stirred at atemperature of between 0° and 5° C. for 3 hours, during which the pH wascontrolled to between 3 and 4 using a 20% aqueous sodium carbonatesolution.

To this reaction mixture was added1--N-ethylaminobenzene-3-β-sulfatoethylsulfone (27.8 parts) which hadbeen prepared from 1-aminobenzene-3-β-sulfatoethylsulfone anddiethylsulfuric acid in a conventional manner, and then the resultingmixture was heated to 40° C. while the pH being controlled to between 5and 6 using a 20% aqueous sodium carbonate solution, and stirred for 25hours at this temperature. To the reaction mixture was added sodiumchloride to produce crystals, which were then collected on asuction-filter, washed and then dried at 60° C. Thus, a copper formazancompound represented by a free acid of the following formula wasobtained. ##STR19##

EXAMPLE 2

Example 1 was repeated, provided that each amine described below wasused in place of 1-N-ethylamino benzene-3-β-sulfatoethylsulfone in thesame molar amount as in Example 1, whereby the corresponding copperformazan compound having λ_(max) value of 612±2 nm was

    ______________________________________                                        Run                                                                           No.     Amine [Compound of the formula (III)]                                 ______________________________________                                        1       1-N-Ethylaminobenzene-4-β-sulfatoethylsulfone                    2       1-N-Ethylaminobenzene-2-β-sulfatoethylsulfone                    3       1-N-Ethylamino-4-methoxybenzene-3-β-sulfato-                             ethylsulfone                                                          4       1-N-Methylaminobenzene-3-β-sulfatoethyl-                                 sulfone                                                               5       1-N-Methylaminobenzene-4-β-sulfatoethylsulfone                   6       1-N-Methylaminobenzene-2-β-sulfatoethylsulfone                   7       1-N-Methylamino-4-methoxybenzene-3-β-sulfato-                            ethylsulfone                                                          8       1-N-β-Carbamoylethylaminobenzene-3-β-sulfato-                       ethylsulfone                                                          9       1-N-β-Carbamoylethylaminobenzene-2-β-sulfato-                       ethylsulfone                                                          10      1-N-β-Carbamoylethylaminobenzene-4-β-sulfato-                       ethylsulfone                                                          11      1-N-β-Carbamoylethylamino-4-methoxybenzene-3-                            β-sulfatoethylsulfone                                            12      1-N-n-Propylaminobenzene-3-β-sulfatoethyl-                               sulfone                                                               13      1-N-n-Propylaminobenzene-4-β-sulfatoethyl-                               sulfone                                                               14      1-N-n-Propylaminobenzene-2-β-sulfatoethyl-                               sulfone                                                               15      1-N-n-Propylamino-4-methoxybenzene-3-β-                                  sulfatoethylsulfone                                                   16      1-N-β-Cyanoethylaminobenzene-3-β-sulfato-                           ethylsulfone                                                          17      1-N-β-Cyanoethylaminobenzene-4-β-sulfato-                           ethylsulfone                                                          18      1-N-β-Cyanoethylaminobenzene-2-β-sulfato-                           ethylsulfone                                                          19      1-N-β-Cyanoethylamino-4-methoxybenzene-3-β-                         sulfatoethylsulfone                                                   20      1-N-β-Hydroxyethylaminobenzene-3-β-sulfato-                         ethylsulfone                                                          21      1-N-β-Hydroxyethylaminobenzene-4-β-sulfato-                         ethylsulfone                                                          22      1-N-β-Hydroxyethylaminobenzene-2-β-sulfato-                         ethylsulfone                                                          23      1-N-β-Hydroxyethylamino-4-methoxybenzene-3-β-                       sulfatoethylsulfone                                                   24      1-N-β-Sulfoethylaminobenzene-3-β-sulfato-                           ethylsulfone                                                          25      1-N-β-Methoxycarbonylethylaminobenzene-3-                                β-sulfatoethylsulfone                                            26      1-N-β-Carboxyethylaminobenzene-3-β-sulfato-                         ethylsulfone                                                          27      1-N-Ethylamino-2-methoxybenzene-5-β-sulfato-                             ethylsulfone                                                          28      1-N-Ethylamino-2,4-dimethylbenzene-5-β  -sulfato-                        ethylsulfone                                                          29      1-N-Ethylamino-2-methoxy-5-methylbenzene-4-β-                            sulfatoethylsulfone                                                   30      1-N-Ethylamino-4-methylbenzene-3-β-sulfato-                              ethylsulfone                                                          31      2-N-Ethylaminonapthhalene-6-β-sulfatoethyl-                              sulfone                                                               32      2-N-Ethylamino-8-sulfonaphthalene-6-β-                                   sulfatoethylsulfone                                                   33      2-N-Methylaminonaphthalene-8-β-sulfatoethyl-                             sulfone                                                               ______________________________________                                    

EXAMPLE 3

Run No. I of Example 2 was repeated, provided that each amine describedbelow was used in place of 1-N-ethylaminobenzene-4-β-sulfatoethylsulfonein the same molar amount as in Run No. 1 of Example 2, whereby thecorresponding copper formazan compound was obtained.

    ______________________________________                                        Run                                                                           No.     Amine Compound of the formula (III)                                   ______________________________________                                        1       1-N-Ethylaminobenzene-4-vinylsulfone                                  2       1-N-Ethylaminobenzene-4-β-chloroethylsulfone                     3       1-N-Ethylaminobenzene-4-β-acetoxyethylsulfone                    4       1-N-Ethylaminobenzene-4-β-phosphato-                                     ethylsulfone                                                          5       1-N-Ethylaminobenzene-4-β-thiosulfato-                                   ethylsulfone                                                          ______________________________________                                    

EXAMPLE 4

Example 1 was repeated, provided that2-carboxyphenylhydrazine-4-sulfonic acid was used in place of2-carboxyphenylhydrazine-5-sulfonic acid in the s amount thereof,whereby a copper formazan compound represented by a free acid of thefollowing formula was obtained. ##STR20##

EXAMPLE 5

Example 4 was repeated, provided that the same amines as those used inRun Nos. 1 to 33 of Example 2 were used respectively in place of1-N-ethylamino- benzene-3-β-sulfatoethylsulfone, whereby thecorresponding copper formazan compounds having λ_(max) of 618±2 nm wereobtained.

EXAMPLE 6

The copper formazan compound (0.1, 0.3 and 0.6 part) obtained in Example1 was dissolved respectively in water (200 parts) to prepare each dyeliquor. Sodium sulfate (10 parts) and cotton (10 parts) were added toeach dye liquor, which was then heated to 60° C. At this temperature,sodium carbonate (4 parts) was added, and the dyeing was continued for 1hour.

Thereafter, the dyed cotton was washed with water, soaped, then washedwith water and dried. Thus, a dyed product of a brilliant blue colorhaving excellent fastness, particularly excellent fastness to light,perspiration-light and chlorine with good dischargeability, wasobtained.

The above formazan compound revealed good build-up and level-dyeingproperties, solubility and reproducibility.

For the comparison purpose, the above dyeing was repeated, provided thata dye (A) of the formula, ##STR21## which is disclosed in Example 1 ofPublished Unexamined Japanese Patent Application No. 4783/1981, wasused.

The results are as shown in the following Table 1.

                  TABLE 1                                                         ______________________________________                                        Comparison of dyeing depth                                                    in 60° C. dyeing                                                                Dye concentration                                                    Compound   1% o.w.f.   3% o.w.f.                                                                              6% o.w.f.                                     ______________________________________                                        Compound of                                                                              100%        100%     100%                                          Example 1                                                                     Dye (A)     61%         30%      16%                                          ______________________________________                                    

Dyeing depth shown in Table 1 is expressed in such a manner that thedyeing depth in dye concentration of the dyed product obtained using thedye (A) was compared with that of the dyed product obtained using thecompound of Example 1, which was evaluated as 100%.

Table 1 demonstrates that the copper formazan compound of the presentinvention is superior in build-up property to the known dye (A).

EXAMPLE 7

The dyeing was carried out using each copper formazan compound obtainedin Examples 2 to 5 in the same manner as in Example 6, whereby eachcompound revealed similar results.

EXAMPLE 8

A diazonium compound-containing mixture obtained by subjecting a neutralsolution containing sodium 3-acetylamino-2-hydroxyaniline-5-sulfonate(24.6 parts, on the acid basis) to diazotization in a conventionalmanner, was added at a pH of between 12 and 13 to an aqueous solutioncontaining a hydrazone (30.6 parts) obtained from2-methoxy-5-sulfophenyl-hydrazine and benzaldehyde, and the resultingmixture was kept at a pH of between 12 and 13 by the addition of sodiumhydroxide. After completion of the coupling reaction, to thisoxy-methoxy-formazan-containing solution was poured a solutionconsisting of crystalline copper sulfate (25 parts), potassium sodiumtartarate tetrahydrate (33.5 parts), a 40% aqueous sodium hydroxidesolution (63 parts) and water (250 parts). The mixture was refluxed for5 hours at 100° C. to effect complex formation and hydrolysis of theacetylamino group simultaneously under demethylation.

To this reaction mixture, sodium chloride and potassium chloride wereadded in each amount of 10% by weight based on the volume of thereaction mixture, and the mixture was cooled and then adjusted to pH 0.5by the dropwise addition of hydrochloric acid. The aminoformazancompound formed was collected on a filter.

The product obtained was suspended in water, and the suspension wasadjusted to pH 7 by the addition of sodium hydroxide, cooled to 0° C.and then mixed with cyanuric chloride (18.5 parts). The mixture was keptat a pH of between 5 and 6 using a 20% aqueous sodium carbonatesolution, and then 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone (27.8parts) was added thereto. The resulting mixture was heated to 40° C.while controlling the pH to between 5 and 6 by the addition of a 20%aqueous sodium carbonate solution, and then stirred overnight at thistemperature. Thereafter, the reaction mixture was mixed with sodiumchloride and then filtered to separate a product, which was washed andthen dried. Thus, a copper formazan compound represented by a free acidof the following formula was obtained. ##STR22##

EXAMPLE 9

Example 1 was repeated, provided that 2-sulfobenzaldehyde was used inplace of benzaldehyde in the same molar amount as in Example 1, wherebya copper formazan compound represented by a free acid of the followingformula was obtained ##STR23##

EXAMPLE 10

According to the same manner as in Example 8, provided that the sameamines as used in Run Nos. 1 to of Example 2 are used respectively inplace of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone, eachcorresponding copper formazan compound can be obtained. According to thesame manner as in Example 9, provided that the same amines as used inRun Nos. 1 to 33 of Example 2 are used respectively in place of1-N-ethylaminobenzene-3-8-sulfatoethylsulfone, each corresponding copperformazan compound can be obtained.

EXAMPLE 12

The dyeing was carried out in the same manner as in Example 6, providedthat the copper formazan compound of Example 8 was used, whereby a dyedproduct of a brilliant yellowish blue color having excellent chlorine,perspiration-light and light fastness and excellent dischargeabilitywith high build-up property was obtained.

The above formazan compound was also found to be superior in that a dyedproduct constant in the quality was able to be obtained irrespective ofchange in the dyeing temperature.

According to the same manner as above, provided that the copper formazancompounds in Example 10 are used, similar results can be obtained.

EXAMPLE 13

The dyeing was carried out in the same manner as in Example 6, providedthat the copper formazan compound obtained in Example 9 was used,whereby a dyed product of a brilliant blue color having excellentproperties was obtained. Similar results can be obtained when the copperformazan compounds described in Example 11 are used.

EXAMPLE 14

Disodium salt ofN-(2-carboxy-5-sulfophenyl)-N-(2'-hydroxy-3'-amino-5'-sulfophenyl)-ms-phenylformazancopper complex (59.7 parts, on the acid basis) obtained in the samemanner as in Example 1 was dissolved in water (500 parts). To thissolution cooled to 0° C. was dropwise added2,4,6-trifluoro-1,3,5-triazine (13.5 parts), while controlling the pH to6 by the addition of a 15% aqueous sodium carbonate solution. Aftercompletion of the condensation reaction,1-N-ethylaminobenzene-3-β-sulfatoethylsulfone (27.8 parts) was addedthereto. The temperature was raised to 20° C. while controlling the pHto between 5 and 6 by the addition of a 15% aqueous sodium carbonatesolution, and the condensation reaction was continued at thattemperature and at that pH. Sodium chloride was added to the reactionmixture to precipitate the product, which was collected on asuction-filter, washed and then dried at 40° C. Thus, a copper formazancompound represented by a free acid of the following formula wasobtained. ##STR24##

EXAMPLE 15

Example 14 was repeated, provided that theN-(2-carboxy-5-sulfophenyl)-N-(2'-hydroxy-3'-amino-5'-sulfophenyl)-ms-phenylformazan copper complex and the1-N-ethylaminobenzene-3-β-sulfatoethylsulfone were replaced with thecompounds shown in the columns I [Formazan compound of the formula(II)]and II [Amine compound of the formula (III)], respectively, wherebyeach corresponding copper formazan compound was obtained.

    __________________________________________________________________________    Run                                                                              Column I [Formazan compond of                                                                    Amine column II [Compound of the                        No.                                                                              the formula (II)]  formula (III)]                                          __________________________________________________________________________    1  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-4-β-sulfato-                    hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             ethylsulfone                                               phenylformazan copper complex                                              2  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-3-β-sulfato-                    hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             ethylsulfone                                               phenylformazan copper complex                                              3  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-β-Carbamoylethylaminobenzene-                     hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             3-β-sulfatoethylsulfone                               phenylformazan copper complex                                              4  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-β-Hydroxyethylaminobenzene-3-                     hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             β-sulfatoethylsulfone                                 phenylformazan copper complex                                              5  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-n-Propylaminobenzene-3-β-                         hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             sulfatoethylsulfone                                        phenylformazan copper complex                                              6  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-Methylaminobenzene-4-β-                           hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             sulfatoethylfulfone                                        phenylformazan copper complex                                              7  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-2-β-sulfato-                    hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             ethylsulfone                                               phenylformazan copper complex                                              8  N-(2-carboxy-4-sulfophenyl)-N-(2'-                                                               1-N-Ethylamino-4-methoxybenzene-3-                         hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             β-sulfatoethylsulfone                                 phenylformazan copper complex                                              9  N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-4-βsulfato-                     hydroxy-3'-amino-5'-sulfophenyl)-                                                                ethylsulfone                                               ms-phenylformazan copper complex                                           10 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-β-Carbamoylethylaminobenzene-3-                   hydroxy-3'-amino-5'-sulfophenyl)-                                                                β-sulfatoethylsulfone                                 ms-phenylformazan copper complex                                           11 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-β-Hydroxyethylaminobenzene-3-                     hydroxy-3'-amino-5'-sulfophenyl)-                                                                β-sulfatoethylsulfone                                 ms-phenylformazan copper complex                                           12 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-n-Propylaminobenzene-3-β-                         hydroxy-3'-amino-5'-sulfophenyl)-                                                                sulfatoethylsulfone                                        ms-phenylformazan copper complex                                           13 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-Methylaminobenzene-4-β-                           hydroxy-3'-amino-5'-sulfophenyl)-                                                                sulfatoethylsulfone                                        ms-phenylformazan copper complex                                           14 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-2-β-sulfato-                    hydroxy-3'-amino-5'-sulfophenyl)-                                                                ethylsulfone                                               ms-phenylformazan copper complex                                           15 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-Ethylamino-4-methoxybenzene-3-                         hydroxy-3'-amino-5'-sulfophenyl)-                                                                β-sulfatoethylsulfone                                 ms-phenylformazan copper complex                                           16 N-(2-Hydroxy-5-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-3-β-sulfato-                    hydroxy-3'-amino-5'-sulfophenyl)-                                                                ethylsulfone                                               ms-phenylformazan copper complex                                           17 N-(2-Hydroxy-5-sulfophenyl)-N-(2'-                                                               1-N-β-Carbamoylethylamino-benzene-                    hydroxy-3'-amino-5'-sulfophenyl)-                                                                3-β-sulfatoethylsulfone                               ms-phenylformazan copper complex                                           18 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-Ethylaminobenzene-3-β-                            hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             sulfatoethylsulfone                                        2"-sulfophenylformazan copper complex                                      19 N-(2-Carboxy-5-sulfophenyl)-N-(2'-                                                               1-N-βCarbamoylethylaminobenzene-3-                    hydroxy-3'-amino-5'-sulfophenyl)-ms-                                                             β-sulfatoethylsulfone                                 2"-sulfophenylformazan copper complex                                      20 N-(2-Carboxyphenyl)-N-(2'-hydroxy-3'-                                                            1-N-βCarbamoylethylaminobenzene-3-                    amino-5'-sulfophenyl)-ms-2"-                                                                     β-sulfatoethylsulfone                                 sulfophenylformazan copper complex                                         21 N-(2-Carboxyphenyl)-N-(2'-hydroxy-3'-                                                            1-N-Ethylaminobenzene-3-β-sulfato-                    amino-5'-sulfophenyl)-ms-2"-                                                                     ethylsulfone                                               sulfophenylformazan copper complex                                         __________________________________________________________________________

EXAMPLE 16

Each copper formazan compound obtained in Examples 14 and 15 in eachamount of 0.1, 0.3 and 0.6 part was dissolved in water (200 parts).Sodium sulfate (10 parts) and cotton (10 parts) were added to the dyeliquor, which was then heated to 50° C. Thereafter, sodium carbonate (4parts) was added thereto, and the dyeing was carried out for 1 hour atthat temperature. The dyed cotton was washed with water, soaped, againwashed with water and then dried. Thus, each dyed product of a brilliantblue color having excellent fastness and dischargeability was obtainedwith a high build-up property. Each formazan compound was found to besuperior in that a dyed product constant in the quality was able to beobtained irrespective of change in the dyeing temperature.

For the comparison purpose, the above dyeing was repeated, provided thata dye (B) of the following formula, ##STR25## which is disclosed inExample 1, No. 80, of Published Unexamined Japanese Patent ApplicationNo. 12187/1980, was used.

From this comparison, it was found that the copper formazan compoundobtained in Example 14 was superior to the known dye (B), particularlyin buildup property and solubility.

EXAMPLE 17

2-Amino-4-nitrophenol-6-sulfonic acid (23.4 parts) was diazotized, andthen the pH of the diazo liquor was adjusted to between 6 and 7. Thehydrozone compound (32.0 parts) obtained in the same manner as inExample 4 was added to the above diazo liquor, and then an aqueoussolution containing crystalline copper sulfate (26.2 parts) was addedthereto. The resulting mixture was stirred for several hours at atemperature of between 0° C. and 10° C. and a pH of between 6 and 7. Thereaction mixture was adjusted to a pH of about 1 using hydrochloricacid, then stirred for 1 hour, and neutralized with sodium hydroxide.Thus, a formazan compound represented by a free acid of the followingformula was obtained. ##STR26## This compound was subjected to hydrazinereduction in a conventional manner, converting the nitro group appendedto the above compound to the amino group. The resulting amino compoundwas allowed to react with cyanuric chloride and1-N-ethylaminobenzene-4-β-sulfatoethylsulfone in order in a mannersimilar to that of Example 1, whereby a copper formazan compoundrepresented by a free acid of the following formula was obtained.

EXAMPLE 18

In a manner similar to that of Example 1, a diazonium compound of2-aminophenol-4-sulfonic acid (18.9 parts) and an aqueous solutioncontaining crystalline copper sulfate (25 parts) were simultaneouslyadded to a hydrozone compound (37.7 parts) obtained from5-acetylamino-2-aminobenzoic acid and benzaldehyde-2-sulfonic acid, andthe resulting mixture was kept at a temperature of between 0° and 10° C.The mixture was adjusted to a pH of between 8 and 9 and then stirred for5 hours at that temperature. After heating to 60° C., the mixture wasmixed with a 28% aqueous ammonia (100 parts), and then stirred for 2hours to obtain a formazan compound represented by a free acid of theformula, ##STR27##

This compound was subjected to alkali hydrolysis in a conventionalmanner, converting the acetylamino group to the amino group.

The resulting amino compound was allowed to react with cyanuric chlorideand 1-N-β-carbamoyl ethylaminobenzene-3-β-sulfatoethylsulfone in orderin a manner similar to that of Example 1, whereby a copper formazancompound represented by a free acid of the following formula wasobtained. ##STR28##

EXAMPLE 19

According to a manner similar to those of Examples 1, 17 and 18,excepting using the compounds as shown in the following table, eachcopper formazan compound capable of dyeing cotton fiber in a color asshown in the following table can be obtained.

      Run No. Compound of formula (V) Compound of formula (VI) Compound of     formula (VII) Compound of formula (III) Color on cellulose      1     ##STR29##      ##STR30##      ##STR31##      ##STR32##      Reddish blue      2     ##STR33##      ##STR34##      "      ##STR35##      Blue      3     ##STR36##      "      ##STR37##      ##STR38##      "      4 "     ##STR39##      ##STR40##      ##STR41##      Reddish blue      5     ##STR42##      ##STR43##      ##STR44##      ##STR45##       Blue      6     ##STR46##      ##STR47##      ##STR48##      ##STR49##      "      7     ##STR50##      ##STR51##      ##STR52##      ##STR53##      "      8     ##STR54##      "      ##STR55##      ##STR56##      Greenish blue      9     ##STR57##      ##STR58##      ##STR59##      ##STR60##      "      10 "     ##STR61##      ##STR62##      ##STR63##      Reddish blue      11 "     ##STR64##      ##STR65##      ##STR66##      Blue      12 "     ##STR67##      ##STR68##      ##STR69##      Reddish blue      13     ##STR70##      ##STR71##      ##STR72##      ##STR73##      Blue      14 "     ##STR74##      ##STR75##      ##STR76##      "      15 "     ##STR77##      ##STR78##      ##STR79##      "      16     ##STR80##      " "      ##STR81##      "      17     ##STR82##      ##STR83##      ##STR84##      ##STR85##      Reddish blue      18     ##STR86##      ##STR87##      ##STR88##      ##STR89##      "

EXAMPLE 20

In a manner similar to that of Example 6, each copper formazan compoundobtained in Examples 17 and 18 was used to obtain each dyed product of ablue color having excellent fastness, particularly against light,perspiration-light and chlorine. The above compounds were also found tobe superior in build-up and level-dyeing properties, solubility andreproducibility of the dyeing.

Likewise, favorable results can be obtained when the copper formazancompounds described in Example 19 are used.

What is claimed is:
 1. A compound represented by a free acid of theformula, ##STR90## wherein A₁ and A₂ are independently phenyleneunsubstituted or substituted with one substituent selected from thegroup consisting of chlorine, bromine, nitro, methyl ethyl, methoxy,ethoxy sulfonyl, N,N-dimethylsulfamoyl, B is phenyl unsubstituted orsubstituted with one or two members selected from the group consistingof chlorine, methyl ethyl, methoxy, ethoxy, carbomethoxy, carboethoxy,and nitro, Me is a copper ion, X is --O--, or ##STR91## Y is fluorine orchlorine, Z is sulfonic acid, carboxylic acid or phorphoric acid, eachof l, m and and n is 0 or an integer of 1 to 3, provided that the sum ofI, m and n is from 2 to 3, D is phenylene unsubstituted or substitutedwith one or two members selected from the group consisting of methyl,ethyl, methoxy, ethoxy, chlorine and bromine, or nephthyleneunsubstituted or substituted with sulfonic acid group, R is lower alkylunsubstituted or substituted with hydroxy, carboxy, sulfo, carbamoyl,cyano or methoxycarbonyl, and Q is --SO₂₃ CH═CH₂ or --SO₂ CH₂ CH₂ OSO₃H.
 2. A compound represented by a free acid of the formula, ##STR92##wherein R is lower alkyl unsubstituted or substituted with hydroxy,carboxy, sulfo, carbamoyl, cyano or methoxycarbonyl, D₁ methoxy, ethoxy,chlorine or bromine, or naphthylene unsubstituted or substituted withsulfonic acid group, Q is --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ OSO₃ H, Y₁ isfluorine or chlorine, and each of p, q and r is 0 or 1, provided thatthe sum of p, q and r is from 2 to
 3. 3. A compound represented by thefree acid of the formula, ##STR93## wherein R is lower alkylunsubstituted or substituted with hydroxy, carboxy, sulfo, carbamoyl,cyano or methoxycarbonyl, D₁ is phenylene unsubstituted or substitutedwith methyl, ethyl, methoxy, ethoxy group, chlorine or bromine, ornaphthylene unsubstituted or substituted with sulfonic acid group, Q is--SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ OSO₃ H, Y₁ is a fluorine or chlorine atom,and each of p and q is 0 or
 1. 4. A compound represented by a free acidof the formula, ##STR94## wherein R₁ is a methyl, ethyl, carbamoylethyl,hydroxyethyl or n- or iso-propyl group, and Q is --SO₂ CH═CH₂ SO₂ CH₂CH₂ OSOhd 3H.
 5. A compound represented by a free acid of the formula,##STR95##
 6. A compound represented by a free acid of the formula,##STR96##
 7. A compound represented by a free acid of the formula,##STR97##
 8. A compound represented by a free acid of the formula,##STR98##